Benzotriazole UV absorbers being substituted in the benzo ring by electron withdrawing moieties exhibit enhanced durability and low loss rates when incorporated into automotive coatings and thermoplastic compositions.
The benzotriazoles have long been an important class of UV absorbers and have gained wide commercial importance and acceptance for many industrial applications. The prior art is replete with references to their manufacture and utility. However, as requirements become ever more stringent and demanding, the search for still more stable and durable benzotriazoles continues. The gradual phase out of HAPS solvents, such as xylene, because of environmental concerns and their replacement with non-HAPS solvents, such as esters, ethers or ketones, and increased durability requirements for automotive coatings make this search more urgent Indeed, the automotive industry is most concerned about UVA losses from automotive paints and coatings as seen in the publication by J. L. Gerlock et al., Proc. 36th Annual Tech. Sym. (Cleveland Coating Society), May 18, 1993.
Vysokomol Soedin, Ser. A, 18(3), 553 (1976) describes the linear dependence of hydrogen bond strength and photostability in benzotriazoles.
J. E. Pickett et al., Angew. Makromol. Chem. 232, 229 (1995) describe the photodegradation of benzotriazole UV absorbers in poly(methyl methacrylate) films. Structural variation generally caused only small differences in the rates of degradation unless the substitution disrupted the intramolecular hydrogen bonds which are critical for stability. Pickett et al. did not test any benzotriazoles containing both electron withdrawing and electron donating groups as in the instant invention.
J. Catalan et al., J. Am. Chem. Soc., 114, 964 (1992) and H. J. Heller, Eur. Polymer J. Suppl. 1969, 105 both suggest that a bulky substituent such as tert-butyl ortho to the hydroxy group on the phenyl ring will increase stability in highly polar systems.
The prior art leads one to the conclusion that strengthening the hydrogen bond leads to a more stable benzotriazole, but does not teach how this can be accomplished. The instant invention discloses benzotriazoles which exhibit enhanced durability, but surprisingly this enhanced durability is not always related to greater hydrogen bond strength. Indeed, compounds with enhanced durability often have weaker, not stronger hydrogen bonds.
U.S. Pat. Nos. 4,226,763; 4,278,589; 4,315,848; 4,275,004; 4,347,180; 5,554,760; 5,563,242; 5,574,166 and 5,607,987 describe selected benzotriazoles, substituted in the 3-position of the hydroxyphenyl ring by an xcex1-cumyl group, which show very good durability in automotive coatings. These benzotriazoles represent the present state of the art. The instant invention is directed at preparing benzotriazoles which exhibit still better durability and low loss rates from the prior art benzotriazoles.
U.S. Pat. Nos. 5,278,314; 5,280,124; 5,436,349 and 5,516,914 describe red-shifted benzotriazoles. These benzotriazoles are substituted in the 3-position of the phenyl ring with an xcex1-cumyl group and at the 5-position of the benzo ring by thio ethers, alkylsulfonyl or phenylsulfonyl moieties. Red-shifting the benzotriazoles is desirable for spectral reasons. A group at the 5-position which is also electron withdrawing provides additional benefits in low loss rates and durability as found in the instant invention. Missing from these patents are any alkylsulfones with seven or fewer carbon atoms. When such sulfonyl substituents are combined with specifically xcex1-cumyl moieties, extremely durable compounds result which, due to the bulk of the xcex1-cumyl moiety have sufficiently low volatility to be useful in coating and other polymer systems.
The presence of an xcex1-cumyl or phenyl group ortho to the hydroxy group on the phenyl ring exerts a surprisingly large positive effect on benzotriazole photostability in coatings and photographic gel systems. The magnitude of this effect, particularly when compared to a tert-butyl group in that position, is well beyond prediction. The combination of both an electron withdrawing group on the benzo ring and an xcex1-cumyl or phenyl group on the phenyl ring in the same molecule leads to extremely desirable properties in coating systems when high UV absorber permanence is critical.
Novel compounds meeting these parameters as being extremely stable in aggressive use environments constitute a first portion of this invention.
The presence of the electron withdrawing moiety at the 5-position of the benzo ring has a powerful stabilizing effect on benzotriazoles in general and is observed in other polymer systems such as polycarbonate and poly(vinyl chloride) substrates as well. However, the effect of having an xcex1-cumyl or phenyl group ortho to the hydroxy moiety on the phenyl ring is much smaller to non-existent in some polymer systems such as polycarbonate or poly(vinyl chloride) even though critical for coating systems as described above.
In addition to being more photostable, the compounds of this invention are red-shifted, absorbing strongly in the 350-400 nm wavelength range. While such red-shifting is desirable in that a greater portion of the UV spectrum is absorbed, this can also introduce color if the absorption beyond 400 nm is significant. This can limit the use of such compounds, particularly in systems such as polycarbonate glazing applications or present difficulties in various pigmented systems.
It is found that the nature of the substituent ortho to the hydroxyl group on the phenyl ring has an unexpected impact on color imparted to the substrate by the benzotriazole. Thus, relatively subtle differences in substitution on the phenyl ring can have a large impact on the resulting color and the applicability of the benzotriazole in specific color sensitive applications. There are striking differences between having hydrogen, alkyl or xcex1-cumyl at this 3-position.
Furthermore, it is found that, when the 5-position of the benzo ring is substituted with a trifluoromethyl group, the resulting benzotriazole not only exhibits the same or greater enhanced stability when incorporated into thermoplastic resins, but also imparts less color than related benzotriazoles substituted at the 5-position with other electron withdrawing moieties such as sulfonyl or carbonyl. These trifluoromethyl compounds also absorb strongly in the 350-400 nm wavelength range despite the low color and are extremely compatible in a wide range of substrates such as acrylic resins, hydrocarbons, polycarbonates and poly(vinyl chloride).
There are a multitude of general references to benzotriazoles having in the 5-position of the benzo ring electron withdrawing groups such as esters, amides, sulfones and the like that are not substituted in the 3-position of the phenyl ring by an xcex1-cumyl or phenyl moiety. In many of these references the broadly described compounds are unexemplified and no teaching or appreciation taught of the positive effect on photostability described in this invention. In any event, the vast majority of these structures fall well outside the scope of instant invention.
Perfluoroalkyl, specifically trifluoromethyl, is an ideal substituent for the 5-position of the benzo ring. The prior art relevant to this substituent is very limited and exemplifies none of the instant compounds. As a result, said prior art naturally fails to point out the important advantages regarding stability, color and compatibility achievable with the 5-trifluoromethyl substituted benzotriazoles of this invention. The general, unexemplified references to alkyl substituted with halogen are acknowledged, but are clearly irrelevant to the instant invention.
German Offen. 1,670,951 describes inter alia the use of methylene (or alkylidene) bis-benzotriazoles substituted with electron withdrawing groups in polymeric resins. Especially useful are the asymmetrical compounds where only one benzotriazole moiety is substituted. Such asymmetric compounds have considerably less color.
German 116,320 provides a method of preparing benzotriazole N-oxide intermediates which can be converted into dyes and light stabilizers. The N-oxide of 5-trifluoromethyl-2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole is disclosed. This N-oxide could be reduced to the corresponding benzotriazole which is substituted at the 5-position of the phenyl ring. However, this benzotriazole is clearly outside the scope of the instant claims. Other related light stabilizer intermediates are generically disclosed in this reference, but none where ever converted to actual benzotriazole UV absorbers. The outstanding properties of such benzotriazole UV absorbers clearly went undiscovered.
Japanese Hei 3-57690 claims a color developer sheet compositions containing salicylic acid salts and benzotriazoles. Broadly described are benzotriazoles which may be substituted on the benzo ring with unspecified trihalomethyl. However, other benzotriazole ring substituents also are broadly described to include unspecified alkyl, alkoxy, aryloxy, amino, cyano, acyl, nitro and halogen. The only benzotriazoles named as typical examples are either unsubstituted on the benzo ring or substituted by chlorine. The preference is for liquid compounds. The 3-position of the phenyl ring is specified as tert-alkyl. While this reference broadly discloses a wide variety of benzotriazole derivatives in its photographic compositions many are electron donating and produce compounds which are in photostability inferior not only to the instant compounds, but also to standard unsubstituted benzotriazoles. No examples or differentiation between within this diverse array is seen. Further, while generic trihalomethyl is described, no compounds of this description are shown or further described in any way. Additionally, trichloro, tribromo and triiodo compounds are clearly outside the scope of the instant invention.
Japanese Sho 47-15210 describes resin compositions containing selected benzotriazoles substituted by a fluorinated alkyl. The generic structures allows for a fluorinated alkyl, but not necessarily perfluorinated alkyl, to be added to either or both the benzo or phenyl rings at any position (the substituents are floating in the generial formula). Non-fluorinated substituents, one on each ring, are defined as hydrogen, halogen, hydroxy, alkyl and alkoxy with no other more specific description. The exemplified resins are poly(vinyl chloride), polycarbonate, ABS and nylon. Seven compounds are specifically exemplified all outside the scope of the instant invention plus one composition containing 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole. No physical data or synthesis for any of these seven compounds are given.
The seven compounds exemplified in the Japanese reference are given below:
a. 2-(2-hydroxy-4-trifluoromethylphenyl)-2H-benzotriazle;
b. 5-methyl-2-(2-hydroxy-4-trifluoromethylphenyl)-2H-benzotriazole;
c. 5-methoxy-2-(2-hydroxy-4-trifluoromethylphenyl)-2H-benzotriazole;
d. 5-chloro-2-(2-hydroxy-4-trifluoromethylphenyl)-2H-benzotriazole;
e. 5-peroxymethoxy-2-(2-hydroxy-4-methylphenyl)-2H-benzotriazole;
f. 5-perfluorooctyl-2-(2-hydroxy-4-methylphenyl)-2H-benzotriazole; and
g. 5-perfluorooctyl-2-(2-hydroxy-4-trifluoromethylphenyl)-2H-benzotriazole.
There are several distinct differences between the disclosure of this Japanese reference and the instant invention. First all the exemplified compounds of the Japanese reference are substituted in the 4-position of the phenyl ring by groups other than hydrogen. The reference allows for substitution of either fluoroalkyl or fluoroalkoxy on any site on either ring as a means of providing for an improved UV absorber. Data given in this application shows this teaching to be inaccurate. Electron withdrawing moieties on the phenyl ring as found in a, b, c, d, and g above, are shown to provide compounds with less durability than unsubstituted derivatives as seen in Example 77. Spectral coverage in the red region is also compromised as seen in Example 74. Significantly, 2-(2-hydroxy-5-trifluoromethylphenyl)-2H-benzotriazole which is very similar to compound a above, is blue-shifted relative to benzotriazoles such as 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole as seen in Example 74. Blue-shifting is undesirable since the need for coverage in the 350-400 nm region is critical for UV absorbers.
An electron donating group at the 5-position of the benzo ring such as the ether compound c above reduces stability as seen in Example 77. While the Japanese reference states fluoroalkyl or fluoroalkoxy radical leads to enhanced stability under light, the instant invention shows that it is the electron withdrawing nature of the group at the 5-position on the benzo ring that confers greater photostability. No such inference in seen in the Japanese reference, and the electron donating ether even a fluorinated ether is counterindicated for enhanced stability.
Furthermore, all examples in the Japanese reference bear only one substituent on the phenyl ring and that is specifically at the 4-position. The instant invention specifically claims only hydrogen at the 4-position as substitution at the 4-position brings undesirable consequences for the use of these compounds in many applications. The compound f is the closest to the instant invention, but it is substituted by a 4-methyl group. As seen in Example 79, substitution of the phenyl ring by an electron donating group at the 5-position diminishes photostability in coatings. Pickett et al. report the same loss of durability for such compounds in thermoplastics. The electron donating characteristics of methyl are less pronounced, but are still similar to alkoxy. The "sgr"p value, as measure of the electronic effect of substituents for aromatic methoxy substitution is xe2x88x920.27 while for methyl is xe2x88x920.17 (March J. xe2x80x9cAdvanced Organic Chemistryxe2x80x9d, 2nd Ed (1977), McGraw-Hill, New York, p 253).
While the generic disclosure of the Japanese reference overlaps formula I of the instant application no such compound is specifically disclosed in the Japanese reference. As mentioned above, all examples of the Japanese reference are substituted at the 4-position of the phenyl ring, most contain the electron withdrawing CF3 group at the 4-position. Compounds of the instant invention explicitly denote hydrogen at the 4-position of the phenyl ring for reasons including color and stability, and expressly designate the 5-position of the benzo ring as the location of the perfluoroalkyl moiety for reasons of stability and spectral coverage.
U.S. Pat. Nos. 3,936,305; 4,681,905; 4,684,679; 4,684,680 and 5,108,835 teach the 2,2xe2x80x2-methylene-bis[4-hydrocarbyl-6-(benzotriazol-2-yl)phenols] having high molar activities and low volatility. In addition U.S. Pat. Nos. 5,292,890 and 5,360,850 teach that asymmetrical bis-benzotriazoles display higher solubility in organic non-polar solvents that the symmetrical dimers made from the same benzotriazole monomer.
U.S. Pat. No. 5,166,355 describes a process for making 2,2xe2x80x2-methylene-bis[6-(benzotriazol-2-yl)-4-hydrocarbylphenol] or 5,5xe2x80x2-methylene-bis(2-hydroxy-4-alkoxybenzophenone) using bis(dialkylamino)methane.
Related bis-benzotriazoles of the instant invention substituted at one or at both of the benzotriazole rings by perfluoroalkyl are unknown and provide the same improvement to these bis-benzotriazoles as mentioned above, namely enhanced durability and broader spectral coverage. Substitution of only one of the benzotriazole moieties in these bis-benzotriazoles by perfluoroalkyl gives the additional advantage of much lower color than the disubstituted compound, indeed nearly to the color of the bis-benzotriazole not substituted by perfluoroalkyl.
The instant invention pertains to novel benzotriazole UV absorbers having enhanced stability and durability and a low loss rate when incorporated into automotive coatings. These new benzotriazole UV absorbers are also soluble in a variety of substrates including thermoplastic polymers and often are essentially colorless even though absorbing in the 350-390 nm range.
More specifically, the instant invention pertains to new benzotriazole compounds of formula I, I, II or IV 
wherein
G1 is hydrogen or chloro,
G2 is cyano, perfluoroalkyl of 1 to 12 carbon atoms, fluoro, xe2x80x94COxe2x80x94G3, xe2x80x94COOG3, xe2x80x94CONHG3, xe2x80x94CON(G3)2, E3SOxe2x80x94 or E3SO2xe2x80x94,
G3 is hydrogen, straight or branched chain alkyl of 1 to 24 carbon atoms, straight or branched chain alkenyl of 2 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, phenyl, or said phenyl or said phenylalkyl substituted on the phenyl ring by 1 to 4 alkyl of 1 to 4 carbon atoms,
G6 is perfluoroalkyl of 1 to 12 carbon atoms,
G7 is hydrogen or perfluoroalkyl of 1 to 12 carbon atoms,
E1 is hydrogen, straight or branched chain alkyl of 1 to 24 carbon atoms, straight or branched chain alkenyl of 2 to 24 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, phenyl, or said phenyl or said phenylalkyl substituted on the phenyl ring by 1 to 4 alkyl of 1 to 4 carbon atoms; or E1 is alkyl of 1 to 24 carbon atoms substituted by one or two hydroxy groups,
E2 and E2xe2x80x2 are independently straight or branched alkyl chain of 1 to 24 carbon atoms, straight or branched chain alkenyl of 2 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, phenyl, or said phenyl or said phenylalkyl substituted on the phenyl ring by one to three alkyl of 1 to 4 carbon atoms; or E2 and E2xe2x80x2 are independently said alkyl of 1 to 24 carbon atoms or said alkenyl of 2 to 18 carbon atoms substituted by one or more xe2x80x94OH, xe2x80x94OCOE11, xe2x80x94OE4, xe2x80x94NCO, xe2x80x94NH2, xe2x80x94NHCOE11, xe2x80x94NHE4 or xe2x80x94N(E4)2, or mixtures thereof, where E4 is straight or branched chain alkyl of 1 to 24 carbon atoms; or said alkyl or said alkenyl interrupted by one or more xe2x80x94Oxe2x80x94, xe2x80x94NHxe2x80x94 or xe2x80x94NE4xe2x80x94 groups or mixtures thereof and which can be unsubstituted or substituted by one or more xe2x80x94OH, xe2x80x94OE4 or xe2x80x94NH2 groups or mixtures thereof;
n is 1 or 2,
when n is 1, E5 is Cl, OE6 or NE7E8, or
E5 is xe2x80x94PO(OE12)2, xe2x80x94OSi(E11)3 or xe2x80x94OCOxe2x80x94E11, or straight or branched chain C1-C24alkyl which is interrupted by xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94 or xe2x80x94NE11 and which can be unsubstituted or substituted by xe2x80x94OH or xe2x80x94OCOxe2x80x94E11, C5-C12 cycloalkyl which is unsubstituted or substituted by xe2x80x94OH, straight chain or branched C2-C18alkenyl which is unsubstituted or substituted by xe2x80x94OH, C7-C15aralkyl, xe2x80x94CH2xe2x80x94CHOHxe2x80x94E13 or glycidyl,
E6 is hydrogen, straight or branched chain C1-C24alkyl which is unsubstituted or substituted by one or more OH, OE4 or NH2 groups, or xe2x80x94OE6 is xe2x80x94(OCH2CH2)wOH or xe2x80x94(OCH2CH2)wOE21 where w is 1 to 12 and E21 is alkyl of 1 to 12 carbon atoms,
E7 and E8 are independently hydrogen, alkyl of 1 to 18 carbon atoms, straight or branched chain C3-C18alkyl which is interrupted by xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94 or xe2x80x94NE11xe2x80x94, C5-C12cycloalkyl, C6-C14aryl or C1-C3hydroxylalkyl, or E7 and E8 together with the N atom are a pyrrolidine, piperidine, piperazine or morpholine ring, or
E5 is xe2x80x94Xxe2x80x94(Z)pxe2x80x94Yxe2x80x94E15 
wherein
X is xe2x80x94Oxe2x80x94 or xe2x80x94N(E16)xe2x80x94,
Y is xe2x80x94Oxe2x80x94 or xe2x80x94N(E17)xe2x80x94,
Z is C2-C12-alkylene, C4-C12-alkylene interrupted by one to three nitrogen atoms, oxygen atoms or a mixture thereof, or is C3-C12-alkylene, butenylene, butynylene, cyclohexylene or phenylene, each substituted by a hydroxyl group,
m is zero, 1 or 2,
is 1, or p is also zero when X and Y are xe2x80x94N(E16)xe2x80x94 and xe2x80x94N(E17)xe2x80x94, respectively,
E15 is a group xe2x80x94COxe2x80x94C(E18)xe2x95x90C(H)E19 or, when Y is xe2x80x94N(E17)xe2x80x94, forms together with E17 a group xe2x80x94COxe2x80x94CHxe2x95x90CHxe2x80x94COxe2x80x94, wherein E18 is hydrogen or methyl, and E19 is hydrogen, methyl or xe2x80x94COxe2x80x94Xxe2x80x94E20, wherein E20 is hydrogen, C1-C12-alkyl or a group of the formula 
wherein the symbols E1, G2, X, Z, m and p have the meanings defined above, and E16 and E17 independently of one another are hydrogen, C1-C12-alkyl, C3-C12-alkyl interrupted by 1 to 3 oxygen atoms, or is cyclohexyl or C7-C15aralkyl, and E16 together with E17 in the case where Z is ethylene, also forms ethylene,
when n is 2, E5 is one of divalent radicals xe2x80x94Oxe2x80x94E9xe2x80x94Oxe2x80x94 or xe2x80x94N(E11)xe2x80x94E10xe2x80x94N(E11)xe2x80x94,
E9 is C2-C8alkylene, C4-C8alkenylene, C4alkynylene, cyclohexylene, straight or branched chain C4-C10alkylene which is interrupted by xe2x80x94Oxe2x80x94 or by xe2x80x94CH2xe2x80x94CHOHxe2x80x94CH2xe2x80x94Oxe2x80x94E14xe2x80x94Oxe2x80x94CH2xe2x80x94CHOHxe2x80x94CH2xe2x80x94,
E10 being straight or branched chain C2-C12alkylene which may be interrupted by xe2x80x94Oxe2x80x94, cyclohexylene, or 
or E10 and E11 with the two nitrogen atoms form a piperazine ring,
E14 is straight or branched chain C2-C8alkylene, straight or branched chain C4-C10alkylene which is interrupted by xe2x80x94Oxe2x80x94, cycloalkylene, arylene or 
where E7 and E8 are independently hydrogen, alkyl of 1 to 18 carbon atoms or E7 and E8 together are alkylene of 4 to 6 carbon atoms, 3-oxapentamethylene, 3-iminopentamethylene or 3 -methyliminopentamethylene,
E11 is hydrogen, straight or branched chain C1-C18alkyl, C5-C12cycloalkyl, straight or branched chain C2-C18alkenyl, C6-C14aryl or C7-C15aralkyl,
E12 is straight or branched chain C1-C18alkyl, straight or branched chain C3-C18alkenyl, C5-C10cycloalkyl, C6-C16aryl or C7-C15aralkyl,
E13 is H, straight chain or branched C1-C18alkyl which is substituted by xe2x80x94PO(OR12)2, phenyl which is unsubstituted or substituted by OH, C7-C15aralkyl or xe2x80x94CH2OE12,
E3 is alkyl of 1 to 20 carbon atoms, hydroxyalkyl of 2 to 20 carbon atoms, alkenyl of 3 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, aryl of 6 to 10 carbon atoms or said aryl substituted by one or two alkyl of 1 to 4 carbon atoms or 1,1,2,2-tetrahydroperfluoroalkyl where the perfluoroalkyl moiety is of 6 to 16 carbon atoms,
L is alkylene of 1 to 12 carbon atoms, alkylidene of 2 to 12 carbon atoms, benzylidene, p-xylylene, xcex1,xcex1,xcex1xe2x80x2,xcex1xe2x80x2-tetramethyl-m-xylylene or cycloalkylidene, and
T is xe2x80x94SOxe2x80x94, xe2x80x94SO2xe2x80x94, xe2x80x94SOxe2x80x94Exe2x80x94SOxe2x80x94, xe2x80x94SO2xe2x80x94Exe2x80x94SO2xe2x80x94, xe2x80x94COxe2x80x94, xe2x80x94COxe2x80x94COxe2x80x94, xe2x80x94COxe2x80x94CH2xe2x80x94COxe2x80x94, xe2x80x94COxe2x80x94Exe2x80x94COxe2x80x94, xe2x80x94COOxe2x80x94Exe2x80x94OCOxe2x80x94 or xe2x80x94COxe2x80x94NG5xe2x80x94Exe2x80x94NG5xe2x80x94COxe2x80x94,
where E is alkylene of 2 to 12 carbon atoms, cycloalkylene of 5 to 12 carbon atoms, or alkylene interrupted or terminated by cyclohexylene of 8 to 12 carbon atoms;
G5 is G3 or hydrogen, and
with the proviso that when T is xe2x80x94SOxe2x80x94, xe2x80x94SO2xe2x80x94, xe2x80x94SOxe2x80x94Exe2x80x94SOxe2x80x94 or xe2x80x94SO2xe2x80x94Exe2x80x94SO2xe2x80x94, E1 is not hydrogen, straight or branched chain alkyl of 1 to 24 carbon atoms, cycloalkyl of 5 to 12 carbon atoms or phenylalkyl of 7 to 15 carbon atoms; or when E3 is alkyl of 1 to 6 carbon atoms, E1 is not hydrogen or phenyl, and the sum of E1 plus E2 is equal to or greater than 8; and when E3 is alkyl of 8 to 18 carbon atoms or alkenyl of 2 to 24 carbon atoms, E1 is not hydrogen, straight or branched chain of 1 to 24 carbon atoms, cycloalkyl of 5 to 12 carbon atoms or phenylalkyl of 7 to 15 carbon atoms; or when G2 is cyano, xe2x80x94COxe2x80x94G3.xe2x80x94CONHG3, xe2x80x94CON(G3)2 or xe2x80x94COOG3, then E1 is phenyl or phenylalkyl of 7 to 15 carbon atoms, or said phenyl or said phenylalkyl substituted on the phenyl ring by 1 to 4 alkyl of 1 to 4 carbon atoms; or when E1 is hydrogen, E2 is not methyl.
Preferably, the new benzotriazole is a compound of formula I 
wherein
G1 is hydrogen,
G2 is cyano, CF3xe2x80x94, fluoro, xe2x80x94COxe2x80x94G3 or E3SO2xe2x80x94,
G3 is straight or branched chain alkyl of 1 to 24 carbon atoms, straight or branched chain alkenyl of 2 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, phenyl, or said phenyl or said phenylalkyl substituted on the phenyl ring by 1 to 4 alkyl of 1 to 4 carbon atoms,
E1 is phenylalkyl of 7 to 15 carbon atoms, phenyl, or said phenyl or said phenylalkyl substituted on the phenyl ring by 1 to 4 alkyl of 1 to 4 carbon atoms,
E2 is straight or branched alkyl chain of 1 to 24 carbon atoms, straight or branched chain alkenyl of 2 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, phenyl, or said phenyl or said phenylalkyl substituted on the phenyl ring by 1 to 3 alkyl of 1 to 4 carbon atoms; or E2 is said alkyl of 1 to 24 carbon atoms or said alkenyl of 2 to 18 carbon atoms substituted by one or more xe2x80x94OH, xe2x80x94OCOE11, xe2x80x94OE4, xe2x80x94NCO, xe2x80x94NH2, xe2x80x94NHCOE11, xe2x80x94NHE4 or xe2x80x94N(E4)2, or mixtures thereof, where E4 is straight or branched chain alkyl of 1 to 24 carbon atoms; or said alkyl or said alkenyl interrupted by one or more xe2x80x94Oxe2x80x94, xe2x80x94NHxe2x80x94 or xe2x80x94NE4xe2x80x94 groups or mixtures thereof and which can be unsubstituted or substituted by one or more xe2x80x94OH, xe2x80x94OE4 or xe2x80x94NH2 groups or mixtures thereof;
E3 is alkyl of 1 to 20 carbon atoms, hydroxyalkyl of 2 to 20 carbon atoms, alkenyl of 3 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, aryl of 6 to 10 carbon atoms or said aryl substituted by one or two alkyl of 1 to 4 carbon atoms or 1,1,2,2-tetrahydroperfluoroalkyl where the perfluoroalkyl moiety is of 6 to 16 carbon atoms; or
is a compound of formula I wherein,
G1 is hydrogen,
G2 is CF3xe2x80x94, fluoro or E3SO2xe2x80x94,
E1 is hydrogen or straight or branched alkyl of 4 to 24 carbon atoms,
E2 is as defined above, and
E3 is straight or branched chain alkyl of 1 to 7 carbon atoms,
with the proviso that the sum of the carbon atoms in E1 and E2 is greater than or equal to 8 when G2 is E3SO2.
Preferably, the benzotriazole is also a compound of formula IIIA 
wherein
G1 is hydrogen,
G2 is CF3xe2x80x94 or fluoro,
E1 is hydrogen, straight or branched alkyl of 4 to 24 carbon atoms or phenylalkyl of 7 to 15 carbon atoms,
E5 is xe2x80x94OE6 or xe2x80x94NE7E8, or
E5 is
xe2x80x94Xxe2x80x94(Z)pxe2x80x94Yxe2x80x94E15
wherein
X is xe2x80x94Oxe2x80x94 or xe2x80x94N(E16)xe2x80x94,
Y is xe2x80x94Oxe2x80x94 or xe2x80x94N(E17)xe2x80x94,
Z is C2-C12-alkylene, C4-C12-alkylene interrupted by one to three nitrogen atoms, oxygen atoms or a mixture thereof, or is C3-C12-alkylene, butenylene, butynylene, cyclohexylene or phenylene, each substituted by a hydroxyl group,
m is 0, 1, 2 or 3,
p is 1, or p is also zero when X and Y are xe2x80x94N(E16)xe2x80x94 and xe2x80x94N(E17)xe2x80x94, respectively,
E15 is a group xe2x80x94COxe2x80x94C(E18)xe2x95x90C(H)E19 or, when Y is xe2x80x94N(E17)xe2x80x94, forms together with E17 a group xe2x80x94COxe2x80x94CHxe2x95x90CHxe2x80x94COxe2x80x94, wherein E18 is hydrogen or methyl, and E19 is hydrogen, methyl or xe2x80x94COxe2x80x94Xxe2x80x94E20, wherein E20 is hydrogen, C1-C12-alkyl or a group of the formula. 
Preferably, the benzotriazole is also a compound of formula IV 
wherein
G6 is CF3,
G7 is hydrogen or CF3,
E2 and E2xe2x80x2 are independently straight or branched alkyl chain of 1 to 24 carbon atoms, straight or branched chain alkenyl of 2 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, phenyl, or said phenyl or said phenylalkyl substituted on the phenyl ring by 1 to 3 alkyl of 1 to 4 carbon atoms; and
L is alkylene of 1 to 12 carbon atoms, alkylidene of 2 to 12 carbon atoms, benzylidene, p-xylylene, xcex1,xcex1,xcex1xe2x80x2,xcex1xe2x80x2-tetramethyl-m-xylylene or cycloalkylidene.
Most preferably, the new benzotriazole is a compound of formula I 
wherein
G1 is hydrogen,
G2 is CF3xe2x80x94,
E1 is phenylalkyl of 7 to 15 carbon atoms, phenyl, or said phenyl or said phenylalkyl substituted on the phenyl ring by 1 to 4 alkyl of 1 to 4 carbon atoms,
E2 is straight or branched alkyl chain of 1 to 24 carbon atoms, straight or branched chain alkenyl of 2 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, phenyl, or said phenyl or said phenylalkyl substituted on the phenyl ring by 1 to 3 alkyl of 1 to 4 carbon atoms; or E2 is said alkyl of 1 to 24 carbon atoms or said alkenyl of 2 to 18 carbon atoms substituted by one or more xe2x80x94OH, xe2x80x94OCOE11, xe2x80x94NH2 or xe2x80x94NHCOE11, or mixtures thereof; or said alkyl or said alkenyl interrupted by one or more xe2x80x94Oxe2x80x94 which can be unsubstituted or substituted by one or more xe2x80x94OH groups; or
is a compound of formula I wherein,
G6 is hydrogen,
G2 is CF3xe2x80x94,
E1 is hydrogen, straight or branched alkyl of 4 to 24 carbon atoms or phenylalkyl of 7 to 15 carbon atoms, and
E2 is as defined above.
Most preferably, the benzotriazole is also a compound of formula IIIA 
wherein
G1 is hydrogen,
G2 is CF3xe2x80x94,
E1 is hydrogen, straight or branched alkyl of 4 to 24 carbon atoms or phenylalkyl of 7 to 15 carbon atoms,
E5 is xe2x80x94OE6 or xe2x80x94NE7E8 where
E6 is hydrogen, straight or branched chain C1-C24alkyl which is unsubstituted or substituted by one or more OH groups, or xe2x80x94OE6 is xe2x80x94(OCH2CH2)wOH or xe2x80x94(OCH2CH2)wOE21 where w is 1 to 12 and E21 is alkyl of 1 to 12 carbon atoms, and
E7 and E8 are independently hydrogen, alkyl of 1 to 18 carbon atoms, straight or branched chain C3-C18alkyl which is interrupted by xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94 or xe2x80x94NE11xe2x80x94, C5-C12cycloalkyl, C6-C14aryl or C1-C3hydroxylalkyl, or E7 and E8 together with the N atom are a pyrrolidine, piperidine, piperazine or morpholine ring.
Most preferably, the benzotriazole is also a compound of formula IV 
wherein
G6 is CF3,
G7 is hydrogen or CF3,
E2 and E2xe2x80x2 are independently straight or branched alkyl chain of 1 to 24 carbon atoms, straight or branched chain alkenyl of 2 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, phenyl, or said phenyl or said phenylalkyl substituted on the phenyl ring by 1 to 3 alkyl of 1 to 4 carbon atoms; and
L is methylene.
Compounds which are especially preferred are:
(a) 5-trifluoromethyl-2-(2-hydroxy-3-xcex1-cumyl-5-tert-octylphenyl)-2H-benzotriazole;
(b) 5-trifluoromethyl-2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole;
(c) 5-trifluoromethyl-2-(2-hydroxy-3,5-di-tert-octylphenyl)-2H-benzotriazole;
(d) 2,2xe2x80x2-methylene-bis[6-(5-trifluoromethyl-2H-benzotriazol-2-yl)-4-tert-octyl-phenol];
(e) methylene-2-[4-tert-octyl-6-(2H-benzotriazol-2-yl)phenol]2xe2x80x2-[4-tert-octyl-6-(5-trifluoromethyl-2H-benzotriazol-2-yl)phenol];
(f) 3-(5-trifluoromethyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamic acid;
(g) methyl 3-(5-trifluoromethyl-2H-benzotriazol-2-yl)-5-tert-butyl4-hydroxyhydrocinnamate;
(h) isooctyl 3-(5-trifluoromethyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate;
(i) 5-trifluoromethyl-2-[2-hydroxy-5-(3-hydroxypropyl)phenyl]-2H-benzotriazole;
(j) 5-trifluoromethyl-2-[2-hydroxy-5-(3-acryloyloxypropyl)phenyl]-2H-benzotriazole;
(k) 5-trifluoromethyl-2-[2-hydroxy-5-(3-methacryloyloxypropyl)phenyl]-2H-benzotriazole;
(l) 5-trifluoromethyl-2-[2-hydroxy-5-(3-acrylylaminopropyl)phenyl]-2H-benzotriazole;
(m) 5-trifluoromethyl-2-[2-hydroxy-5-(3-methacrylylaminopropyl)phenyl]-2H-benzotriazole;
(n) 5-trifluoromethyl-2-(2-hydroxy-3-xcex1-cumyl-5-tert-butylphenyl)-2H-benzotriazole;
(o) 5-trifluoromethyl-2-(2-hydroxy-3-xcex1-cumyl-5-nonylphenyl)-2H-benzotriazole;
(p) 5-trifluoromethyl-2-[2-hydroxy-3-xcex1-cumyl-5-(2-hydroxyethyl)phenyl]-2H-benzotriazole;
(q) 5-trifluoromethyl-2-[2-hydroxy-3-xcex1-cumyl-5-(3-hydroxypropyl)phenyl]-2H-benzotriazole;
(r) 5-trifluoromethyl-2-(2-hydroxy-3,5-ditert-amylphenyl)-2H-benzotriazole;
(s) 5-trifluoromethyl-2-(2-hydroxy-3,5-ditert-butylphenyl)-2H-benzotriazole;
(t) 5-trifluoromethyl-2-(2-hydroxy-3-dodecyl-5-methylphenyl)-2H-benzotriazole;
(u) 5-trifluoromethyl-2-[2-hydroxy-3-tert-butyl-5-(3-hydroxypropyl)phenyl)-2H-benzotriazole;
(v) 5-trifluoromethyl-2-[2-hydroxy-3-tert-butyl-5-(2-hydroxyethyl)phenyl]-2H-benzotriazole;
(w) 5-trifluoromethyl-2-[2-hydroxy-5-(2-hydroxyethyl)phenyl]-2H-benzotriazole;
(x) 5-trifluoromethyl-2-(2-hydroxy-3,5-di-xcex1-cumylphenyl)-2H-benzotriazole;
(y) 5-fluoro-2-(2-hydroxy-3,5-di-xcex1-cumylphenyl)-2H-benzotriazole;
(z) 5-butylsulfonyl-2-(2-hydroxy-3,5-di-xcex1-cumylphenyl)-2H-benzotriazole;
(aa) 5-butylsulfonyl-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole; and
(bb) 5-butylsulfonyl-2-(2-hydroxy-3,5-di-tert-octylphenyl)-2H-benzotriazole.
Examples of these various radicals are as follow:
When any of E1 to E21 is alkyl, such groups are, for example, methyl, ethyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, tert-amyl, 2-ethylhexyl, tert-octyl, lauryl, tert-dodecyl, tridecyl, n-hexadecyl, n-octadecyl and eicosyl; when any of said radicals is alkenyl, such groups are, for example, allyl or oleyl; when any of said radicals is cycloalkyl, such groups are, for example, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and cyclododecyl; when any of said radicals are phenylalkyl, such groups are, for example, benzyl, phenethyl, xcex1-methylbenzyl and xcex1,xcex1-dimethylbenzyl; and when any of said radicals is aryl, they are, for example, phenyl, naphthyl, or when substituted by alkyl are, for example, tolyl and xylyl. When E6 is alkyl substituted by one or more xe2x80x94Oxe2x80x94 groups and/or substituted by one or more xe2x80x94OH, the xe2x80x94OE6 moiety can be xe2x80x94(OCH2CH2)wOH or xe2x80x94(OCH2CH2)wOE21 where w is 1 to 12 and E21 is alkyl of 1 to 12 carbon atoms, for example.
When E is alkylene, it is, for example, ethylene, tetramethylene, hexamethylene, 2-methyl-1,4-tetramethylene, hexamethylene, octamethylene, decamethylene and dodecamethylene; when E is cycloalkylene, it is, for example, cyclopentylene, cyclohexylene, cycloheptylene, cyclooctylene and cyclododecylene; and when E is alkylene interrupted or terminated by cyclohexylene, it is, for example, the saturated diyl radical derived from limonene, herein called dihydrolimonenediyl.
When E is alkylene, it is, for example, ethylene, tetramethylene, hexamethylene, 2-methyl-1,4-tetramethylene, hexamethylene, octamethylene, decamethylene and dodecamethylene; when E is cycloalkylene, it is, for example, cyclopentylene, cyclohexylene, cycloheptylene, cyclooctylene and cyclododecylene; and when E is alkylene interrupted or terminated by cyclohexylene, it is, for example, the saturated diyl radical derived from limonene, herein called dihydrolimonenediyl.
When the instant compounds contain a free carboxyl moiety where E2 is xe2x80x94CH2CH2COOE6 where E6 is hydrogen, the alkali metal or amine salts of said acids are also contemplated as part of this invention allowing such UV absorbers to be used in aqueous systems due to the enhanced water solubility of such instant compounds.
E6, E7 and E8 can be the following C3-C18alkyl radicals which are interrupted by xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, or xe2x80x94NE11xe2x80x94 and can be substituted by OH: methoxyethyl, ethoxyethyl, butoxyethyl, butoxypropyl, methylthioethyl, CH3OCH2CH2OCH2CH2xe2x80x94, CH3CH2OCH2CH2OCH2CH2xe2x80x94, C4H9OCH2CH2OCH2CH2xe2x80x94, ethylthiopropyl, octylthiopropyl, dodecyloxypropyl, 2-hydroxyethyl, 2-hydroxypropyl, 4-hydroxybutyl, 6-hydroxyhexyl, xe2x80x94CH2CH2xe2x80x94NHxe2x80x94C4H9, xe2x80x94CH2CH2CH2NHxe2x80x94C8H17 and xe2x80x94CH2CH2CH2xe2x80x94N(CH3)xe2x80x94CH2CH(C2H5)C4H9,
E6, E7, E8, E11 and E12 can be the following C5-C12cycloallyl radicals: cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl or cyclodecyl. In the case of E6, the radical can also be substituted by xe2x80x94OH.
E7, E8 and E11 can be the following alkenyl radicals: allyl, methallyl, 2-n-hexenyl or 4-n-octenyl.
When E6 is alkenyl, it can have the same meaning as E7, E8 and E11 as alkenyl radicals, but it can also be xe2x80x94CHxe2x95x90CH2, n-undec-10-enyl or n-octadec-9-enyl, and it is also possible for the radical E6 to be substituted by xe2x80x94OH.
E7 and E8 can be the following C7-C15aralkyl radicals: benzyl, xcex1-phenethyl, 2-phenethyl or 4-tert-butylbenzyl.
When E11, E13 or E12 are aralkyl, they can, independently of one another, have the same meaning as E7 or E8.
Independently of one another, E7, E8 and E11 can be the following C6-C14 aryl radicals: phenyl, xcex1-naphthyl or xcex2-naphthyl.
When E7 and E8 are C1-C3 hydroxyalkyl, they can be the following radicals: hydroxymethyl, 2-hydroxyethyl or 2-hydroxypropyl.
As C2-C8 alkylene, E9 and E14 can be the following radicals: ethylene, propylene, butylene, hexylene or octylene.
As alkylene, E10 can be the same radicals, but can, in addition, also be higher-molecular groups such as decylene or dodecylene.
When E9 is a C4-C8alkenylene radical, the following is an example of a suitable group: butenylene.
In the case of E9 and E14, suitable straight or branched chain C4-C10alkylene groups which are interrupted by xe2x80x94Oxe2x80x94 are the following groups: xe2x80x94CH2CH2OCH2CH2xe2x80x94, xe2x80x94CH(CH3)xe2x80x94CH2xe2x80x94Oxe2x80x94CH2xe2x80x94CH(CH3)xe2x80x94CH2CH2OCH2CH2OCH2CH2xe2x80x94 and xe2x80x94CH2CH2OCH2CH2OCH2CH2OCH2CH2xe2x80x94.
When E14 is a cycloalkylene radical, the following groups are embraced: 1,3-cyclohexylene and 1,4-cyclohexylene.
When E14 is arylene, this can be, specifically, the following groups: 1,3-phenylene or 1,4-phenylene.
As C2-C12-alkylene, Z is a straight or branched chain. It is for example: ethylene, propylene, tetramethylene, hexamethylene, octamethylene, dodecamethylene, 1,1-ethylidene, 2,2-propylidene, 2,2-amylidene or 2-ethylhexamethylene. C2-C6-alkylene groups are preferred.
When Z is C4-C12-alkylene which is interrupted by oxygen, it is for example: xe2x80x94CH2xe2x80x94CH213 Oxe2x80x94CHxe2x80x942xe2x80x94CH2xe2x80x94, xe2x80x94CH2xe2x80x94CH2xe2x80x94Oxe2x80x94CH2xe2x80x94CH2xe2x80x94CH2, CH2xe2x80x94CH2xe2x80x94Oxe2x80x94CH2xe2x80x94CH2xe2x80x94Oxe2x80x94CH2xe2x80x94CH2 or xe2x80x94CH2xe2x80x94CH2xe2x80x94Oxe2x80x94CH2xe2x80x94CH2xe2x80x94Oxe2x80x94CH2xe2x80x94CH2xe2x80x94Oxe2x80x94CH2xe2x80x94CH2xe2x80x94, and, when alkylene is interrupted by nitrogen, a group xe2x80x94N(E16)xe2x80x94 is meant, where E16 is as defined in the foregoing, for example xe2x80x94CH2xe2x80x94CH2xe2x80x94NHxe2x80x94CH2xe2x80x94CH2xe2x80x94CH2xe2x80x94CH2, xe2x80x94CH2xe2x80x94CH2xe2x80x94CH2xe2x80x94NHxe2x80x94(CH2)8xe2x80x94 or xe2x80x94CH2CH2xe2x80x94CH2xe2x80x94N(CH3xe2x80x94CH2xe2x80x94CH(C2H5)(CH2)4xe2x80x94.
As C3-C12-alkylene substituted by a hydroxyl group, Z is 2-hydroxytetramethylene, 2-hydroxyhexamethylene and, in particular, 2-hydroxytrimethylene.
As cyclohexylene, Z is for example 1,4cyclohexylene and, in particular, 1,2-cyclohexylene.
As phenylene, Z is for example m-phenylene or p-phenylene.
m can be zero, 1, 2 or 3, but it is preferably 2.
p is preferably 1, but can also be zero if both X and Y are bound by way of nitrogen.
As C1-C8-alkyl, E1 is for example: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, tert-amyl, n-nexyl, n-heptyl, n-octyl, 2-ethylhexyl or tert-octyl. Tert-butyl is preferred.
As C1-C12-alkyl, E16, E17 and E20 can have the same meaning as that given in the foregoing for R1, and can additionally be straight or branched-chain nonyl, decyl, undecyl, or dodecyl.
When E16 and E17 are alkyl interrupted by oxygen atoms, the examples which apply are the same as those described in the foregoing for Z.
Examples for E16 and E17 as aralkyl are: benzyl, xcex1-methylbenzyl, 1-phenylethyl, xcex1,xcex1-dimethylbenzyl or 1-phenylpropyl.
If Z is ethylene, E16 and E17 together can likewise form ethylene, which is equivalent to a bridging over by way of a piperazine group.
When Y is a group xe2x80x94N(E17)xe2x80x94, E15 and E17 together make up a group xe2x80x94COxe2x80x94CHxe2x95x90CHxe2x80x94COxe2x80x94, and thus form the substituent 
on the group xe2x80x94Xxe2x80x94(Z)pxe2x80x94.
The preferred meaning of E15 is, however, xe2x80x94COxe2x80x94C(E18)xe2x95x90CHE14, E18 and E19 are preferably methyl and especially hydrogen.
E2 is xe2x80x94CH2xe2x80x94CH2xe2x80x94Oxe2x80x94COxe2x80x94C(G)xe2x95x90CH2 and G is hydrogen or methyl.
The instant invention also pertains to a composition stabilized against thermal, oxidative or light-induced degradation which comprises,
(a) an organic material subject to thermal, oxidative or light-induced degradation, and
(b) an effective stabilizing amount of a compound of formula I, II, III or IV.
Preferably, the organic material is a natural, semi-synthetic or synthetic polymer, especially a thermoplastic polymer.
Most preferably, the polymer is a polyolefin or polycarbonate, especially polyethylene or polypropylene; most especially polypropylene; or the polymer is a styrenic, ABS, a nylon, a polyester such as poly(ethylene terephthalate) or poly(butylene terephthalate), a polyurethane, an acrylate, a rubber modified styrenic, poly(vinyl chloride), poly(vinyl butyral), polyacetal (polyoxymethylene), poly(ethylene naphthalene-dicarboxylate), or other blends or copolymers such as poly(ethylene/1,4-cyclohexylene-dimethylene terephthalate) PETG or an ionomer as described on page 29.
In another preferred embodiment of the instant invention, the organic material is a resin selected from the group consisting of a thermoset acrylic melamine resin, an acrylic urethane resin, an epoxy carboxy resin, a silane modified acrylic melamine, an acrylic resin with carbamate pendant groups crosslinked with melamine or an acrylic polyol resin crosslinked with melamine containing carbamate groups.
Most preferably, the resin is a thermoset acrylic melamine resin or an acrylic urethane resin.
In yet another preferred embodiment of the instant invention, the organic material is a recording material.
The recording materials according to the invention are suitable for pressure-sensitive copying systems, photocopying systems using microcapsules, heat-sensitive copying systems, photographic materials and ink jet printing.
The recording materials according to the invention are distinguished by an unexpected improvement in quality, especially with regard to the fastness to light.
The recording materials according to the invention have the construction known for the particular use. They consist of a customary carrier, for example, paper or plastic film, which has been coated with one or more layers. Depending on the type of material, these layers contain the appropriate necessary components, in the case of photographic materials, for example, silver halide emulsions, dye couplers, dyes and the like. Material particularly suitable for ink jet printing has a layer particularly absorptive for ink on a customary carrier. Uncoated paper can also be employed for ink jet printing. In this case the paper acts at the same time as the carrier material and as the ink-absorbent layer. Suitable material for ink jet printing is, for example, described in U.S. Pat. No. 5,073,448 which is incorporated herein by reference.
The recording material can also be transparent as, for example, in the case of projection films.
The compounds of formula I, II, III or IV can be incorporated into the carder material as early as the production of the latter, in the production of paper, for example, being added to the paper pulp. A second method of application is to spray the carder material with an aqueous solution of compounds of formula I, II, III or IV or to add the compounds to the coating composition.
Coating compositions intended for transparent recording materials suitable for projection cannot contain any particles which scatter light, such as pigments and fillers.
The dye-binding coating composition can contain a number of other additives, for example, antioxidants, light stabilizers (including also UV absorbers which do not fall under the scope of the UV absorbers of this invention), viscosity improvers, fluorescent brighteners, biocides and/or antistatic agents.
The coating composition is usually prepared as follows: the water-soluble components, for example, the binder, are dissolved in water and stirred together, the solid components, for example, fillers and other additives already described, are dispersed in this aqueous medium; and dispersion is advantageously carried out by means of devices, for example, ultrasonic systems, turbine stirrers, homogenizers, colloid mills, bead mills, sand mills, high-speed stirrers and the like. The compounds of formula I, II, III or IV can be easily incorporated into the coating composition.
The recording material according to this invention preferably contains 1 to 5000 mg/m2, in particular 50-1200 mg/m2, of a compound of formula I.
As already mentioned, the recording materials according to the invention embrace a wide field. The compounds of formula I, II, III or IV can, for example, be employed in pressure-sensitive copying systems. They can be introduced either into the paper in order to protect the microencapsulated dye precursors there from light, or into the binder of the developer layer in order to protect the dyes formed there.
Photocopying systems using light-sensitive microcapsules which are developed by means of pressure are described in U.S. Pat. Nos. 4,416,966; 4,483,912; 4,352,200; 4,535,050; 4,535,463; 4,551,407; 4,562,137 and 4,608,330; and also in EP-A 139,479; EP-A 162,664; EP-A 164,931; EP-A 237,024; EP-A 237,025 and EP-A 260,129. In all these systems, the compounds can be put into the dye-receiving layer. The compounds can, however, also be put into the donor layer in order to protect the color formers from light.
Photographic materials which can be stabilized are photographic dyes and layers containing such dyes or precursors thereof, for example, photographic paper and films. Suitable materials are, for example, described in U.S. Pat. No. 5,364,749 which is incorporated herein by reference. The compounds of formula I, II, III or IV act here as a UV filter against electrostatic flashes. In color photographic materials, couplers and dyes are also protected against photochemical decomposition.
The instant compounds can be used for all types of color photographic materials. For example, they can be employed for color paper, color reversal paper, direct-positive color material, color negative film, color positive film, color reversal film and the like. They are preferably used inter alia for photographic color material which contains a reversal substrate or form positives.
Color-photographic recording materials usually contain, on a support, a blue-sensitive and/or a green-sensitive and/or a red-sensitive silver halide emulsion layer and, if desired, a protection layer, with the instant compounds being, preferably, either in the green-sensitive or the red-sensitive layer or in a layer between the green-sensitive and the red-sensitive layer or in a layer on top of the silver halide emulsion layers.
The compounds of formula I, II, III or IV can also be employed in recording materials based on the principles of photopolymerization, photoplasticization or the rupture of microcapsules, or in cases where heat-sensitive and light-sensitive diazonium salts, leuko dyes having an oxidizing agent or dye lactones having Lewis acids are used.
Furthermore, the instant compounds can be employed in recording materials for dye diffusion transfer printing, thermal wax transfer printing and non-matrix printing and for use with electrostatic, electrographic, electrophoretic, magnetographic and laser-electrophotographic printers and pen-plotters. Of the above, recording materials for dye diffusion transfer printing are preferred, for example, as described in EP-A 507,734.
The instant compounds can also be employed in inks, preferably for ink jet printing, for example, as described in U.S. Pat. No. 5,098,477 which is incorporated herein by reference.
The compounds of this invention exhibit superior hydrolytic stability, handling and storage stability as well as good resistance to extractability when present in a stabilized composition.
The methodology to make the instant compounds is described in the prior art. The intermediates needed to make the instant compounds are largely items of commerce.
Preferred compounds are those in which one of X and Y is xe2x80x94Oxe2x80x94; and particularly those in which both X and Y are xe2x80x94Oxe2x80x94.
In general polymers which can be stabilized include
1. Polymers of monoolefins and diolefins, for example polypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyisoprene or polybutadiene, as well as polymers of cycloolefins, for instance of cyclopentene or norbornene, polyethylene (which optionally can be crosslinked), for example high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), branched low density polyethylene (BLDPE).
Polyolefins, i.e. the polymers of monoolefins exemplified in the preceding paragraph, preferably polyethylene and polypropylene, can be prepared by different, and especially by the following, methods:
a) radical polymerisation (normally under high pressure and at elevated temperature).
b) catalytic polymerisation using a catalyst that normally contains one or more than one metal of groups IVb, Vb, VIb or VIII of the Periodic Table. These metals usually have one or more than one ligand, typically oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/or aryls that may be either xcfx80- or "sgr"-coordinated. These metal complexes may be in the free form or fixed on substrates, typically on activated magnesium chloride, titanium(III) chloride, alumina or silicon oxide. These catalysts may be soluble or insoluble in the polymerisation medium. The catalysts can be used by themselves in the polymerisation or further activators may be used, typically metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes, said metals being elements of groups Ia, IIa and/or IIIa of the Periodic Table. The activators may be modified conveniently with further ester, ether, amine or silyl ether groups. These catalyst systems are usually termed Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or single site catalysts (SSC).
2. Mixtures of the polymers mentioned under 1), for example mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (for example PP/HDPE, PP/LDPE) and mixtures of different types of polyethylene (for example LDPE/HDPE).
3. Copolymers of monoolefins and diolefins with each other or with other vinyl monomers, for example ethylene/propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene/but-1-ene copolymers, propylene/isobutylene copolymers, ethylene/but-1-ene copolymers, ethylene/hexene copolymers, ethylene/methylpentene copolymers, ethylene/heptene copolymers, ethylene/octene copolymers, propylene/butadiene copolymers, isobutylene/-isoprene copolymers, ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylate copolymers, ethylene/vinyl acetate copolymers and their copolymers with carbon monoxide or ethylene/acrylic acid copolymers and their salts (ionomers) as well as terpolymers of ethylene with propylene and a diene such as hexadiene, dicyclopentadiene or ethylidene-norbornene; and mixtures of such copolymers with one another and with polymers mentioned in 1) above, for example polypropylene/ethylene-propylene copolymers, LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic acid copolymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or random polyalkylene/carbon monoxide copolymers and mixtures thereof with other polymers, for example polyamides.
4. Hydrocarbon resins (for example C5-C9) including hydrogenated modifications thereof (e.g. tackifiers) and mixtures of polyalkylenes and starch.
5. Polystyrene, poly(p-methylstyrene), poly(xcex1-methylstyrene).
6. Copolymers of styrene or xcex1-methylstyrene with dienes or acrylic derivatives, for example styrene/butadiene, styrene/acrylonitrile, styrene/alkyl methacrylate, styrene/butadiene/alkyl acrylate, styrene/butadiene/alkyl methacrylate, styrene/maleic anhydride, styrene/acrylonitrile/methyl acrylate; mixtures of high impact strength of styrene copolymers and another polymer, for example a polyacrylate, a diene polymer or an ethylene/propylene/diene terpolymer, and block copolymers of styrene such as styrene/butadiene/styrene, styrene/isoprene/styrene, styrene/ethylene/butylene/styrene or styrene/ethylene/propylene/styrene.
7. Graft copolymers of styrene or xcex1-methylstyrene, for example styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile copolymers; styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and methyl methacrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene and maleimide on polybutadiene; styrene and alkyl acrylates or methacrylates on polybutadiene; styrene and acrylonitrile on ethylene/propylene/diene terpolymers; styrene and acrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styrene and acrylonitrile on acrylate/butadiene copolymers, as well as mixtures thereof with the copolymers listed under 6), for example the copolymer mixtures known as ABS, MBS, ASA or AES polymers.
8. Halogen-containing polymers such as polychloroprene, chlorinated rubbers, chlorinated or sulfochlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers, especially polymers of halogen-containing vinyl compounds, for example polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, as well as copolymers thereof such as vinyl chloride/vinylidene chloride, vinyl chloride/vinyl acetate or vinylidene chloride/vinyl acetate copolymers.
9. Polymers derived from xcex1,xcex2-unsaturated acids and derivatives thereof such as polyacrylates and polymethacrylates; polymethyl methacrylates, polyacrylamides and polyacrylonitriles, impact-modified with butyl acrylate.
10. Copolymers of the monomers mentioned under 9) with each other or with other unsaturated monomers, for example acrylonitrile/butadiene copolymers, acrylonitrile/alkyl acrylate copolymers, acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halide copolymers or acrylonitrile/alkyl methacrylate/butadiene terpolymers.
11. Polymers derived from unsaturated alcohols and amines or the acyl derivatives or acetals thereof, for example polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well as their copolymers with olefins mentioned in 1) above.
12. Homopolymers and copolymers of cyclic ethers such as polyalkylene glycols, polyethylene oxide, polypropylene oxide or copolymers thereof with bisglycidyl ethers.
13. Polyacetals such as polyoxymethylene and those polyoxymethylenes which contain ethylene oxide as a comonomer, polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.
14. Polyphenylene oxides and sulfides, and mixtures of polyphenylene oxides with styrene polymers or polyamides.
15. Polyurethanes derived from hydroxyl-terminated polyethers, polyesters or polybutadienes on the one hand and aliphatic or aromatic polyisocyanates on the other, as well as precursors thereof.
16. Polyamides and copolyamides derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams, for example polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides starting from m-xylene diamine and adipic acid; polyamides prepared from hexamethylenediamine and isophthalic or/and terephthalic acid and with or without an elastomer as modifier, for example poly-2,4,4,-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide; and also block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers, e.g. with polyethylene glycol, polypropylene glycol or polytetramethylene glycol; as well as polyamides or copolyamides modified with EPDM or ABS; and polyamides condensed during processing (RIM polyamide systems).
17. Polyureas, polyimides, polyamide-imides and polybenzimidazoles.
18. Polyesters derived from dicarboxylic acids and diols and/or from hydroxycarboxylic acids or the corresponding lactones, for example polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylolcyclohexane terephthalate and polyhydroxybenzoates, as well as block copolyether esters derived from hydroxyl-terminated polyethers; and also polyesters modified with polycarbonates or MBS.
19. Polycarbonates and polyester carbonates.
20. Polysulfones, polyether sulfones and polyether ketones.
21. Crosslinked polymers derived from aldehydes on the one hand and phenols, ureas and melamines on the other hand, such as phenol/formaldehyde resins, urea/formaldehyde resins and melamine/formaldehyde resins.
22. Drying and non-drying alkyd resins.
23. Unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols and vinyl compounds as crosslinking agents, and also halogen-containing modifications thereof of low flammability.
24. Crosslinkable acrylic resins derived from substituted acrylates, for example epoxy acrylates, urethane acrylates or polyester acrylates.
25. Alkyd resins, polyester resins and acrylate resins crosslinked with melamine resins, urea resins, polyisocyanates or epoxy resins.
26. Crosslinked epoxy resins derived from polyepoxides, for example from bisglycidyl ethers or from cycloaliphatic diepoxides.
27. Natural polymers such as cellulose, rubber, gelatin and chemically modified homologous derivatives thereof, for example cellulose acetates, cellulose propionates and cellulose butyrates, or the cellulose ethers such as methyl cellulose; as well as rosins and their derivatives.
28. Blends of the aforementioned polymers (polyblends), for example PP/EPDM, Polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR, PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 and copolymers, PA/HDPE, PA/PP, PA/PPO.
29. Naturally occurring and synthetic organic materials which are pure monomeric compounds or mixtures of such compounds, for example mineral oils, animal and vegetable fats, oil and waxes, or oils, fats and waxes based on synthetic esters (e.g. phthalates, adipates, phosphates or trimellitates) and also mixtures of synthetic esters with mineral oils in any weight ratios, typically those used as spinning compositions, as well as aqueous emulsions of such materials.
30. Aqueous emulsions of natural or synthetic rubber, e.g. natural latex or latices of carboxylated styrene/butadiene copolymers.
31. Polysiloxanes such as the soft, hydrophilic polysiloxanes described, for example, in U.S. Pat. No. 4,259,467; and the hard polyorganosiloxanes described, for example, in U.S. Pat. No. 4,355,147.
32. Polyketimines in combination with unsaturated acrylic polyacetoacetate resins or with unsaturated acrylic resins. The unsaturated acrylic resins include the urethane acrylates, polyether acrylates, vinyl or acryl copolymers with pendant unsaturated groups and the acrylated melamines. The polyketimines are prepared from polyamines and ketones in the presence of an acid catalyst
33. Radiation curable compositions containing ethylenically unsaturated monomers or oligomers and a polyunsaturated aliphatic oligomer.
34. Epoxymelamine resins such as light-stable epoxy resins crosslinked by an epoxy functional coetherified high solids melamine resin such as LSE-4103 (Monsanto).
In general, the compounds of the present invention are employed in from about 0.01 to about 5% by weight of the stabilized composition, although this will vary with the particular substrate and application. An advantageous range is from about 0.05 to about 3%, and especially 0.05 to about 1%. However, some high performance films or in UV absorbing layers of laminates such as those produced by coextrusion may contain from 5-15% by weight of the instant compounds. Concentrations of 5-10% by weight are typical in certain coextrusion applications.
The stabilizers of the instant invention may readily be incorporated into the organic polymers by conventional techniques, at any convenient stage prior to the manufacture of shaped articles therefrom. For example, the stabilizer may be mixed with the polymer in dry powder form, or a suspension or emulsion of the stabilizer may be mixed with a solution, suspension, or emulsion of the polymer. The resulting stabilized polymer compositions of the invention may optionally also contain from about 0.01 to about 5%, preferably from about 0.025 to about 2%, and especially from about 0.1 to about 1% by weight of various conventional additives, such as the materials listed below, or mixtures thereof.
1. Antioxidants
1.1. Alkylated monophenols, for example,
2,6-di-tert-butyl-4-methylphenol
2-tert-butyl-4,6-dimethylphenol
2,6-di-tert-butyl-4-ethylphenol
2,6-di-tert-butyl-4-n-butylphenol
2,6-di-tert-butyl-4-i-butylphenol
2,6-di-cyclopentyl-4-methylphenol
2-(xcex1-methylcyclohexyl)-4,6-dimethylphenol
2,6-di-octadecyl-4-methylphenol
2,4,6-tri-cyclohexylphenol
2,6-di-tert-butyl-4-methoxymethylphenol
1.2. Alkylated hydroquinones, for example,
2,6-di-tert-butyl-4-methoxyphenol
2,5di-tert-butyl-hydroquinone
2,5di-tert-amyl-hydroquinone
2,6diphenyl-4-octadecyloxyphenol
1.3. Hydroxylated thiodiphenyl ethers, for example,
2,2xe2x80x2-thio-bis-(6-tert-butyl4-methylphenol)
2,2xe2x80x2-thio-bis-(4-octylphenol)
4,4xe2x80x2-thio-bis-(6-tert-butyl-3-methylphenol)
4,4xe2x80x2-thio-bis-(6-tert-butyl-2-methylphenol)
1.4. Alkylidene-bisphenols, for example,
2,2xe2x80x2-methylene-bis-(6-tert-butyl-4-methylphenol)
2,2xe2x80x2-methylene-bis-(6-tert-butyl-4-ethylphenol)
2,2xe2x80x2-methylene-bis-[4-methyl-6-(xcex1-methylcyclohexyl)-phenol]
2,2xe2x80x2-methylene-bis-(4-methyl-6-cyclohexylphenol)
2,2xe2x80x2-methylene-bis-(6-nonyl-4-methylphenol)
2,2xe2x80x2-methylene-bis-[6-(xcex1-methylbenzyl)-4-nonylphenol]
2,2xe2x80x2-methylene-bis-[6-(xcex1,xcex1-dimethylbenzyl)-4-nonylphenol]
2,2xe2x80x2-methylene-bis-(4,6-di-tert-butylphenol)
2,2xe2x80x2-ethylidene-bis-(4,6-di-tert-butylphenol)
2,2xe2x80x2-ethylidene-bis-(6-tert-butyl-4isobutylphenol)
4,4xe2x80x2-methylene-bis-(2,6di-tert-butylphenol)
4,4xe2x80x2-methylene-bis-(6-tert-butyl-2-methylphenol)
1,1-bis-(5-tert-butyl4-hydroxy-2-methylphenyl)-butane
2,6-di-(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol
1,1,3-tris-(5-tert-butyl-4-hydroxy-2-methylphenyl)-butane
1,1-bis-(5-tert-butyl4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane
ethyleneglycol bis-[3,3-bis-(3xe2x80x2-tert-butyl-4xe2x80x2-hydroxyphenyl)-butyrate]
di-(3-tert-butyl-4-hydroxy-5-methylphenyl)-dicyclopentadiene
di-[2-(3xe2x80x2-tert-butyl-2xe2x80x2-hydroxy-5xe2x80x2-methyl-benzyl)-6-tert-butyl-4-methylphenyl]terephthalate.
1.5. Benzyl compounds, for example,
1,3,5-tri-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene
di-(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide
3,5-di-tert-butyl-4-hydroxybenzyl-mercapto-acetic acid isooctyl ester
bis-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithiol terephthalate
1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate
1,3,5-tris-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate
3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid dioctadecyl ester
3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid monoethyl ester, calcium-salt
1.6. Acylaminophenols, for example,
4-hydroxy-lauric acid anilide
4-hydroxy-stearic acid anilide
2,4-bis-octylmercapto-6-(3,5-tert-butyl4-hydroxyanilino)-s-triazine
octyl-N-(3,5-di-tert-butyl-4-hydroxyphenyl)-carbamate
1.7. Esters of xcex2-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid with monohydric or polyhydric alcohols, for example,
1.8. Esters of xcex2-(5-tert-butyl-4-hydroxy-3-methylphenyl)-propionic acid with monohydric or polyhydric alcohols, for example,
1.9. Amides of xcex2-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid for example,
N,Nxe2x80x2-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexamethylenediamine
N,Nxe2x80x2-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-trimethylenediamine
N,Nxe2x80x2-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazine
1.10 Diarylamines, for example, diphenylamine, N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine, 4,4xe2x80x2-di-tert-octyl-diphenylamine, reaction product of N-phenylbenzylamine and 2,4,4-trimethylpentene, reaction product of diphenylamine and 2,4,4-trimethylpentene, reaction product of N-phenyl-1-naphthylamine and 2,4,4-trimethylpentene.
2. UV absorbers and light stabilizers
2.1. 2-(2xe2x80x2-Hydroxyphenyl)-benzotriazoles, for example, the 5xe2x80x2-methyl-, 3xe2x80x2,5xe2x80x2-di-tert-butyl-, 5xe2x80x2-tert-butyl-, 5xe2x80x2-(1,1,3,3-tetramethylbutyl)-, 5-chloro-3xe2x80x2,5xe2x80x2-di-tert-butyl-, 5-chloro-3xe2x80x2-tert-butyl-5xe2x80x2-methyl-, 3xe2x80x2-sec-butyl-5xe2x80x2-tert-butyl-, 4xe2x80x2-octoxy, 3xe2x80x2,5xe2x80x2-di-tert-amyl-, 3xe2x80x2,5xe2x80x2-bis-(xcex1,xcex1-dimethylbenzyl), 3xe2x80x2-tert-butyl-5xe2x80x2-(2-(omega-hydroxy-octa-(ethyleneoxy)carbonyl-ethyl)-,3xe2x80x2-dodecyl-5xe2x80x2-methyl-, and 3xe2x80x2-tert-butyl-5xe2x80x2-(2-octyloxycarbonyl)ethyl-, and dodecylated-5xe2x80x2-methyl derivatives.
2.2. 2-Hydroxy-benzophenones, for example, the 4-hydroxy-, 4-methoxy-, 4-octoxy, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy, 4,2xe2x80x2,4xe2x80x2-trihydroxy- and 2xe2x80x2-hydroxy-4,4xe2x80x2-dimethoxy derivatives.
2.3. Esters of optionally substituted benzoic acids for example, phenyl salicylate, 4-tert-butylphenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis-(4-tert-butylbenzoyl)-resorcinol, benzoylresorcinol, 3,5-di-tert-butyl-4-hydroxybenzoic acid 2,4-di-tert-butylphenyl ester and 3,5-di-tert-butyl-4-hydroxybenzoic acid hexadecyl ester.
2.4. Acrylates, for example, xcex1-cyano-xcex2,xcex2-diphenylacrylic acid ethyl ester or isooctyl ester, xcex1-carbomethoxy-cinnamic acid methyl ester, xcex1-cyano-xcex2-methyl-p-methoxy-cinnamic acid methyl ester or butyl ester, xcex1-carbomethoxy-p-methoxy-cinnamic acid methyl ester, N-(xcex2-carbomethoxy-xcex2-cyanovinyl)-2-methyl-indoline.
2.5. Nickel compounds, for example, nickel complexes of 2,2xe2x80x2-thio-bis-[4-(1,1,3,3-tetramethylbutyl)-phenol], such as the 1:1 or 1:2 complex, optionally with additional ligands such as n-butylamine, triethanolamine or N-cyclohexyl-diethanolamine, nickel dibutyldithiocarbamate, nickel salts of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid monoalkyl esters, such as of the methyl, ethyl or butyl ester, nickel complexes of ketoximes such as of 2-hydroxy-4-methyl-phenyl undecyl ketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxy-pyrazole, optionally with additional ligands.
2.6. Sterically hindered amines, for example bis-(2,2,6,6tetramethylpiperidyl)sebacate, bis-(1,2,2,6,6-pentamethylpiperidyl)sebacate, n-butyl-3,5-di-tert.butyl-4-hydroxybenzyl malonic acid bis-(1,2,2,6,6-pentanemethylpiperidyl)ester, condensation product of 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, condensation product of N,Nxe2x80x2-(2,2,6,6-tetramethylpiperidyl)-hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-s-triazine, tris-(2,2,6,6-tetramethylpiperidyl)-nitrilotriacetate, tetrakis-(2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, 1,1xe2x80x2(1,2-ethanediyl)-bis-(3,3,5,5-tetramethylpiperazinone), bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)sebacate.
2.7. Oxalic acid diamides, for example, 4,4xe2x80x2-di-octyloxy-oxanilide, 2,2xe2x80x2-di-octyloxy-5,5xe2x80x2-di-tert-butyl-oxanilide, 2,2xe2x80x2-di-dodecyloxy-5,5xe2x80x2-di-tert-butyl-oxanilide, 2-ethoxy-2xe2x80x2-ethyl-oxanilide, N,Nxe2x80x2-bis (3-dimethylaminopropyl)-oxalamide, 2-ethoxy-5-tert-butyl-2xe2x80x2-ethyloxanilide and its mixture with 2-ethoxy-2xe2x80x2-ethyl-5,4xe2x80x2-di-tert-butyloxanilide and mixtures of ortho- and para-methoxy- as well as of o- and p-ethoxy-disubstituted oxanilides.
2.8. Hydroxyphenyl-s-triazines, for example 2,6-bis-(2,4-dimethylphenyl)-4-(2-hydroxy-4-octyloxyphenyl)-s-triazine; 2,6-bis-(2,4-dimethylphenyl)4-(2,4-dihydroxyphenyl)-s-triazine; 2,4-bis(2,4-dihydroxyphenyl)-6-(4-chlorophenyl)-s-triazine; 2,4-bis[2-hydroxy-4-(2-hydroxy-ethoxy)phenyl]-6-(4-chlorophenyl)-s-triazine; 2,4-bis[2-hydroxy-4-(2-hydroxy-4-(2-hydroxy-ethoxy)phenyl]-6-(2,4-dimethylphenyl)-s-triazine; 2,4-bis[2-hydroxy-4-(2-hydroxyethoxy)-phenyl]-6-(4-bromophenyl)-s-triazine; 2,4-bis[2-hydroxy-4-(2-acetoxyethoxy)phenyl]-6-(4-chlorophenyl)-s-triazine, 2,4-bis(2,4-dihydroxyphenyl)-6-(2,4dimethylphenyl)-s-triazine.
3. Metal deactivators, for example, N,Nxe2x80x2-diphenyloxalic acid diamide, N-salicylal-Nxe2x80x2-salicyloyl-hydrazine, N,Nxe2x80x2-bis-salicyloylhydrazine, N,Nxe2x80x2-bis-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazine, 3-salicyloylamino-1,2,4-triazole, bis-benzylidene-oxalic acid dihydrazide.
4. Phosphites and phosphonites, for example, triphenyl phosphite, diphenylalkyl phosphites, phenyldialkyl phosphites, tri-(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite, di-stearyl-pentaerythritol diphosphite, tris-(2,4-di-tert-butylphenyl) phosphite, di-isodecyl-pentaerythritol diphosphite, di-(2,4,6-tri-tert-butylphenyl)-pentaerythritol diphosphite, di-(2,4-di-tert-butyl-6-methylphenyl)-pentaerythritol diphosphite, di-(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, tristearyl-sorbitol triphosphite, tetrakis-(2,4-di-tert-butylphenyl)4,4xe2x80x2-diphenylylenediphosphonite.
5. Compounds which destroy peroxide, for example, esters of xcex2-thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters, mercapto-benzimidazole or the zinc salt of 2-mercaptobenzimidazole, zinc dibutyl-dithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis-(xcex2-dodecylmercapto)-propionate.
6. Hydroxylamines, for example, N,N-dibenzylhydroxylamine, N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine, N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine, N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecyl-hydroxylamine, N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derived from hydrogenated tallow amine.
7. Nitrones, for example, N-benzyl-alpha-phenyl nitrone, N-ethyl-alpha-methyl nitrone, N-octyl-alpha-heptyl nitrone, N-lauryl-alpha-undecyl nitrone, N-tetradecyl-alpha-tridecyl nitrone, N-hexadecyl-alpha-pentadecyl nitrone, N-octadecyl-alpha-heptadecylnitrone, N-hexadecyl-alpha-heptadecyl nitrone, N-octadecyl-alpha-pentadecyl nitrone, N-heptadecyl-alpha-heptadecyl nitrone, N-octadecyl-alpha-hexadecyl nitrone, nitrone derived from N,N-dialkylhydroxylamine derived from hydrogenated tallow amine.
8. Polyamide stabilizers, for example copper salts in combination with iodides and/or phosphorus compounds and salts of divalent manganese.
9. Basic co-stabilizers, for example, melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids for example Ca stearate, Zn stearate, Mg stearate, Na ricinoleate and K palmitate, antimony pyrocatecholate or zinc pyrocatecholate.
10. Nucleating agents, for example, 4-tert-butyl-benzoic acid, adipic acid, diphenylacetic acid.
11. Fillers and reinforcing agents, for example, calcium carbonate, silicates, glass fibers, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite.
12. Other additives, for example, plasticizers, lubricants, emulsifiers, pigments, optical brighteners, flameproofing agents, anti-static agents, blowing agents and thiosynergists such as dilauryl thiodipropionate or distearyl thiodipropionate.
13. Benzofuranones and indolinones, for example those disclosed in U.S. Pat. Nos. 4,325,863, 4,338,244 or 5,175,312, or 3-[4-(2-acetoxyethoxy)phenyl]-5,7-di-tert-butyl-benzo-furan-2-one, 5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]benzofuran-2-one, 3,3xe2x80x2-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one], 5,7-di-tert-butyl-3-(4-ethoxyphenyl) -benzofuran-2-one, 3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one, 3-(3,5-di-methyl-4-pivaloyloxyphenyl)-5,7-di-tert-butyl-benzofuran-2-one.
The co-stabilizers, with the exception of the benzofuranones listed under 13, are added for example in concentrations of 0.01 to 10%, relative to the total weight of the material to be stabilized.
Further preferred compositions comprise, in addition to components (a) and (b) further additives, in particular phenolic antioxidants, light stabilizers or processing stabilizers.
Particularly preferred additives are phenolic antioxidants (item 1 of the list), sterically hindered amines (item 2.6 of the list), phosphites and phosphonites (item 4 of the list), UV absorbers (item 2 of the list) and peroxide-destroying compounds (item 5 of the list).
Additional additives (stabilizers) which are also particularly preferred are benzofuran-2-ones, such as described, for example, in U.S. Pat. Nos. 4,325,863, 4,338,244 or 5,175,312.
The phenolic antioxidant of particular interest is selected from the group consisting of n-octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, neopentanetetrayl tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinammate), di-n-octadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, thiodiethylene bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), 1,3,5-trimethyl-2,4,6tris(3,5-di-tert-butyl-4-hydroxy-benzyl)benzene, 3,6-dioxaoctamethylene bis(3-methyl-5-tert-butyl-4-hydroxyhydrocinnamate), 2,6di-tert-butyl-p-cresol, 2,2xe2x80x2-ethylidene-bis(4,6-di-tert-butylphenol), 1,3,5-tris(2,6-dimethyl-4-tert-butyl-3-hydroxybenzyl)isocynurate, 1,1,3,-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-tris[2-(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)ethyl]isocyanurate, 3,5-di-(3,5-di-tert-butyl-4-hydroxybenzyl)mesitol, hexamethylene bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), 1-(3,5-di-tert-butyl-4-hydroxyanilino)-3,5-di(octylthio)-s-triazine, N,Nxe2x80x2-hexamethylene-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamamide), calcium bis(ethyl 3,5di-tert-butyl-4-hydroxybenzylphosphonate), ethylene bis[3,3-di(3-tert-butyl-4-hydroxyphenyl)butyrate], octyl 3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate, bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl)hydrazide, and N,Nxe2x80x2-bis[2-(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)-ethyl]-oxamide.
A most preferred phenolic antioxidant is neopentanetetrayl tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), n-octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, 1,3,5-tri-methyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 2,6-di-tert-butyl-p-cresol or 2,2xe2x80x2-ethylidene-bis(4,6-di-tert-butylphenol).
The hindered amine compound of particular interest is selected from the group consisting of bis(2,2,6,6-tetramethylpiperidin-4-yl)sebacate, bis(1,2,2,6,6-pentamethylpiperidin-4-yl)sebacate, di(1,2,2,6,6-pentamethylpiperidin-4-yl)(3,5-di-tert-butyl-4-hydroxybenzyl)butylmalonate, 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triaza-spiro[4.5]decane-2,4-dione, tris(2,2,6,6-tetramethylpiperidin-4-yl) nitrilotriacetate, 1,2-bis(2,2,6,6-tetramethyl-3-oxopiperazin-4-yl)ethane, 2,2,4,4tetramethyl-7-oxa-3,20-diaza-21-oxodispiro[5.1.11.2]heneicosane, polycondensation product of 2,4-dichloro-6-tert-octylamino-s-triazine and 4,4xe2x80x2-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine), polycondensation product of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-hydroxypiperidine and succinic acid, polycondensation product of 4,4xe2x80x2-hexamethylenebis-(amino-2,2,6,6-tetramethylpiperidine) and 1,2-dibromoethane, tetrakis(2,2,6,6-tetramethylpiperidin-4-yl)1,2,3,4-butanetetracarboxylate, tetrakis(1,2,2,6,6-pentamethylpiperidin-4-yl)1,2,3,4-butanetetracarboxylate, polycondensation product of 2,4-dichloro-6-morpholino-s-triazine and 4,4xe2x80x2-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine), N,Nxe2x80x2,Nxe2x80x3,Nxe2x80x2xe2x80x3-tetrakis[(4,6-bis(butyl-1,2,2,6,6-pentamethyl-piperidin-4-yl)-amino-s-triazin-2-yl]-1,10-diamino-4,7-diazadecane, mixed [2,2,6,6-tetramethylpiperidin-4-yl/xcex2,xcex2,xcex2xe2x80x2,xcex2xe2x80x2-tetramethyl-3,9-(2,4,8,10-tetraoxaspiro[5.5]-undecane)diethyl]1,2,3,4-butanetetracarboxylate, mixed [1,2,2,6,6-pentamethylpiperidin4-yl/xcex2,xcex2,xcex2xe2x80x2,xcex2xe2x80x2-tetramethyl-3,9-(2,4,8,10-tetraoxaspiro[5.5]-undecane)diethyl]1,2,3,4-butanetetracarboxylate, octamethylene bis(2,2,6,6-tetramethyl-piperidin-4-carboxylate), 4,4xe2x80x2-ethylenebis(2,2,6,6-tetramethylpiperazin-3-one), N-2,2,6,6-tetramethyl-piperidin-4-yl-n-dodecylsuccinimide, N-1,2,2,6,6-pentamethyl-piperidin-4-yl-n-dodecylsuccinimide, N-1-acetyl-2,2,6,6-tetramethylpiperidin-4-yln-dodecylsuccinimide, 1-acetyl3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione, di-(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)sebacate, di-(1-cyclohexyloxy-2,2,6,6-tetra-methylpiperidin-4-yl)succinate, 1-octyloxy-2,2,6,6-tetramethyl-4-hydroxy-piperidine, poly-{[6-tert-octylamino-s-triazin-2,4-diyl][2-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)imino-hexamethylene-[4-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)imino], and 2,4,6-tris[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)-n-butylamino]-s-triazine.
A most preferred hindered amine compound is bis(2,2,6,6-tetramethylpiperidin-4-yl)sebacate, bis(1,2,2,6,6-pentamethylpiperidin-4-yl)sebacate, di(1,2,2,6,6-pentamethylpiperidin-4-yl)(3,5-di-tert-butyl-4-hydroxybenzyl)butylmalonate, the polycondensation product of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, the polycondensation product of 2,4-dichloro-6-tert-octylamino-s-triazine and 4,4xe2x80x2-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine), N,Nxe2x80x2,Nxe2x80x3,Nxe2x80x2xe2x80x3-tetrakis[(4,6-bis(butyl-(1,2,2,6,6-pentamethylpiperidin-4-yl)amino)-s-triazine-2-yl]-1,10-diamino-4,7-diazadecane.di-(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)sebacate, di-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin4-yl)succinate, 1-octyloxy-2,2,6,6-tetramethyl-4-hydroxy-piperidine, poly-{[6-tert-octylamino-s-triazin-2,4-diyl][2-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)imino-hexamethylene-[4-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)imino], or 2,4,6-tris[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)-n-butylamino]-s-triazine.
The instant composition can additionally contain another UV absorber selected from the group consisting of the benzotriazoles, s-triazines, the oxanilides, the hydroxybenzophenones, benzoates and the xcex1-cyanoacrylates.
Particularly, the instant composition may additionally contain an effective stabilizing amount of at least one other 2-hydroxyphenyl-2H-benzotriazole; another tris-aryl-s-triazine; or hindered amine or mixtures thereof.
Preferably, the 2-hydroxyphenyl-2H-benzotriazole is selected from the group consisting of
2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole;
2-[2-hydroxy-3,5-di(xcex1,xcex1-dimethylbenzyl)phenyl]-2H-benzotriazole;
2-[2-hydroxy-3-(xcex1,xcex1-dimethylbenzyl)-5-tert-octylphenyl]-2H-benzotriazole;
2-{2-hydroxy-3-tert-butyl-5-[2-(omega-hydroxy-octa(ethyleneoxy)carbonyl)ethyl]-phenyl}-2H-benzotriazole;
5-chloro-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole;
5-chloro-2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotriazole;
2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole; and
2-(2-hydroxy-3-tert-butyl-5-[2-(octyloxy)carbonyl)ethyl]phenyl}-2H-benzotriazole.
Preferably, the other tris-aryl-s-triazine is selected from the group consisting of
2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-octyloxyphenyl)-s-triazine;
2,4-diphenyl-6-(2-hydroxy-4-hexyloxyphenyl)-s-triazine; 2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-do-/tri-decyloxy-2-hydroxypropoxy)-phenyl]-s-triazine; and
2-{(2-hydroxyethylamino)-4,6-bis[N-butyl-N-(1-cyclohexyloxy-2,2,6,6-tetramethyl-piperidin4-yl)amino]-s-triazine.
The alkyd resin lacquers which can be stabilized against the action of light and moisture in accordance with the instant invention are the conventional stoving lacquers which are used in particular for coating automobiles (automobile finishing lacquers), for example lacquers based on alkyd/melamine resins and alkyd/acrylic/melamine resins (see H. Wagner and H. F. Sarx, xe2x80x9cLackkunstharzexe2x80x9d (1977), pages 99-123). Other crosslinking agents include glycouril resins, blocked isocyanates or epoxy resins.
The lacquers stabilized in accordance with the invention are suitable both for metal finish coatings and solid shade finishes, especially in the case of retouching finishes, as well as various coil coating applications. The lacquers stabilized in accordance with the invention are preferably applied in the conventional manner by two methods, either by the single-coat method or by the two-coat method. In the latter method, the pigment-containing base coat is applied first and then a covering coat of clear lacquer over it.
It is also to be noted that the compounds of the present invention are applicable for use in non-acid catalyzed thermoset resins such as epoxy, epoxy-polyester, vinyl, alkyd, acrylic and polyester resins, optionally modified with silicon, isocyanates or isocyanurates. The epoxy and epoxy-polyester resins are crosslinked with conventional cross-linkers such as acids, acid anhydrides, amines and the like. Correspondingly, the epoxide may be utilized as the crosslinking agent for various acrylic or polyester resin systems that have been modified by the presence of reactive groups on the backbone structure.
When used in two-coat finishes, the compounds of the instant invention can be incorporated in the clear coat or both in the clear coat and in the pigmented base coat.
When water-soluble, water miscible or water dispersible coating are desired ammonium salts of acid groups present in the resin are formed. Powder coating composition can be prepared by reacting glycidyl methacrylate with selected alcohol components.
The instant benzotriazoles are made by conventional methods for preparing such compounds. The usual procedure involves the diazotization of a substituted o-nitroaniline followed by coupling the resultant diazonium salt with a substituted phenol and reduction of the azobenzene intermediate to the corresponding desired benzotriazole. The starting materials for these benzotriazoles are largely items of commerce or can be prepared by normal methods of organic synthesis.
While the instant benzotriazoles with their enhanced durability are particularly suited for automotive coating applications, it is contemplated that they will also be especially useful in other applications where their enhanced durability is required such as in solar films and the like.